Studies On The Effect Of Non-coordinating Groups Of Ligands On The Structures And Properties Of Metal Complexes

Non-coordinating group, as an important part of the ligand, can not only play an important role in the formation of complexes, but also can exert a deciding influence on their structures and functions (or properties).In this dissertation, Some representative ligands with non-coordination groups were designed and synthesized, and a series of metal complexes with 0D, 1D,2D or 3D structures had been obtained and characterized. The rules of non-coordination groups in governing the framework’s formations of these complexes were studied. Furthermore, EPR spectra, luminescence and magnetic properties of some complexes have been discussed. The main contents have been summarized as follows:1. Eleven AgⅠ, MnⅡ, ZnⅡand CdⅡcomplexes with anthracene-based dicarboxylate and structurally related ligands (anthracene-9,10-dicarboxylic acid H2L1, anthracene-1,5-dicarboxylic acid H2L2, anthracene-1,8-dicarboxylic acid H2L3, anthracene-9,10-dione L4, 9,10-dioxo-9,10-dihydroanthracene-1,8-dicarbonitrile L5, 9,10-dioxo-9,10-dihydroanthracene-1,8-dicarboxylic acid H2L6, 9,10-dioxo-9,10-dihydroanthracene-1,5-dicarboxylic acid H2L7 and benzene-1,2,3-tricarboxylic acid H3L8) and corresponding auxiliary ligands (4,4’-bipyridine L9, 1,10-phenanthroline L10 and 1,3-di(4-pyridyl)propane L11) were synthesized and characterized. Moreover, the luminescent properties of the ZnⅡand CdⅡcomplexes and the corresponding ligands have been investigated at room temperature.2. Five carboxylic acids bearing different bulky skeletons (phenanthrene-9-carboxylic acid HL12,2-phenylquinoline-4-carboxylic acid HL13, adamantane-1-carboxylic acid HL14, biphenyl-4-carboxylic acid HL15 and 3,3-diphenylpropanoic acid HL16)and their twenty three CuⅡ, ZnⅡ, CdⅡ, MnⅡ, CoⅡand NiⅡcomplexes were designed and synthesized with corresponding auxiliary ligands (4,4’-bipyridine L9, 1,10-phenanthroline L10, 2,2’-bipyridine L17, 1,4-diazabicyclo[2.2.2]octane L18, pyrazine L19, hexamethylenetetramine L20, 1,4-diazepane L21 and 3-(2-pyridyl)pyrazole HL22). Furthermore, the EPR spectra of the CuⅡcomplexes and the magnetic properties of the MnⅡand CoⅡcomplexes have been studied. And the luminescent properties of the ZnⅡand CdⅡcomplexes and the corresponding ligands have also been investigated at room temperature.3. Three N-donor ligands with benzimidazole and pyridine rings (l-(2-pyridylmethyl)-1#-benzimidazole L24, 1-(3-pyridylmethyl)-1H-benzimidazole L25 and 1-(4-pyridylmethyl)-1H-benzimidazole L26) were designed and synthesized. Five ZnⅡ, CdⅡand HgⅡcomplexes have been synthesized and structurally characterized. Moreover, the UV-Vis and luminescent spectra of the ZnⅡand HgⅡcomplexes and the corresponding ligands have been investigated at room temperature.The results show that the non-coordination group plays an important role in affecting the structures and properties of complexes.